Metallized azo dyes containing a 2-aminophenoldisulfonamide diazo component



Uited States Patent METALLIZED AZO DYES CQNTAINING A Z-AMl-NOPHENGLDHSULFUNAMlDE DIAZO COMPO= NEWS.

William H. Armenia, Albany, and William E. Wallace, Rensselaer, N.Y.,assignors to General Aniline & Film Corporation, New York, N.Y., acorporation of Delaware No Drawing. Filed Dec. 20, 196i Ser. No. 77,0d9

3 Claims. (Cl. 260-147) This invention relates to the production ofnovel premetallized azo dyestuffs, and more particularly to suchdyestuffs employing as the diazo component the 2-an1inophenoldisulfonamide of the formula 1 was} wherein R and R have thevalues given below. This compound and its method of production isdisclosed and claimed in our copending application Serial No. 704,241,filed on December 23, 1957, now US. Patent 2,979,503.

The novel azo dyestufis of the instant invention may be defined as thecomplex compounds of chromium or cobalt with an azo dyestuff devoid offree sulfionic and carboxylic acid groups and having the formula whereinR and R are selected from the group consisting of H, lower alkyl andhydroxyalkyl of no more than 6 carbon atoms, cyclohexyl, benzyl, phenyl,biphenyl, and when taken together, morpholinyl, piperidinyl and pyridyl;and B represents the radical of a member selected from the groupconsisting of phenolic, naphtholic, and enolic coupling components,containing the hydroxy group in o-rtho position to the azo group. Thepremetallized dyestuffs of the above formula have been found toconstitute a group of valuable dyestur'is which are suitable for dyeinganimal fibers such as silk, leather, and Wool, and nitrogen-containingsynthetic organic polymeric fibers such as the super polyamides (nylon),super polyurethanes, polyacrylonitriles (Acrilan, Zefran, Creslan andthe like) and similar fibers to produce level dyeings having very goodWash and light fastness properties.

in the above formula, R and R may be the same or different, and may beH, alkyl such as octadecyl, decyl, and preferably lower alkyl such asmethyl, ethyl, propyl,

iisobutyl, and hexyl, cycloalkyl such as cyclohexyl, aralkyl such asbenzyl, aryl such as phenyl and biphenyl, and

when taken together, morpholinyl, piperidinyl, pyridyl, and the like. itWill be understood that R and R as above defined may contain inertsubstituents such as hydroxy, lower alkoxy such as methoxy, and thelike.

The dyestuffs of the instant invention may be readily prepared in knownmanner by diazotizing said Z-aminophenoldisulfonamides and coupling thediazotized compound with one of the above defined known couplingcomponents capable of coupling in ortho position relative to the OHgroup.

Such coupling components are well known in the art, including forexample the coupling component B as described and claimed in US.2,551,056 and 2,756,223. They may in general'oe characterized asaromatic (heterocyclic or carbocyclic) compounds containing an active"ice methylene group adjacent to an enolizable keto group, or anaromatic hydroxy or similar group inducing coupling in ortho positionrelative thereto. Such compounds are typified by the acylacetarylides(eg. anilides, etc), the pyrazolones, and aromatic hydroXy compoundscapable of coupling. The preferred coupling components includesphenolic, naphtholic and enolic coupling components capable of couplingin ortho position to the hydroXy group.

As acylacetarylides there may be mentioned acetoacetic acid arylides,such as acetoacetanilide, furoyl acetic acid arylides,terephthaloyl-bis-acetic acid arylides, and the like. As pyrazolones,there may be mentioned l-pheny-l- S-methyl-S-pyrazolone, lp-tolyl-3methy1-5-pyrazolone, B-methyl-S-pyrazolone, S-pyrazolone,1,3-dimethyl-5-pyrazolone, l-(p-chlorophenyl)-3-methyl-5-pyrazolone, l-(2,5'-dichlorophenyl)-3-methyl-5-pyrazolone, l (3-sulfonamidophenyl) 3methyl 5 pyrazolone, l-(p-nitrophenyl -3-mcthyl-5-pyrazolone, 1-o-methoxyphenyl) -3- methyl-S-pyrazolone, l-methyl-S-pyrazolone,l-phenyl-S- pyrazolone, l phenyl 5 pyrazolone -3 carboxylic acid methylester, l-phenyl-5-pyrazolone-3-carboxylic acid ethyl ester, and other -5pyrazolones either unsubstituted or substituted in the 1- and/ or3-positions by non-solubilizing radicals. The aromatic (carbocyclic orheterocyclic) hydroxy compounds useful as coupling components hereincontain a nil-clearly substituted hydroXy group inducing coupling inortho position thereto and generally include phenols, resorcinols, land2-naphthols, including 8- acetoamido-2-naphthol and4,6-dihydroxy-2-naphth-alenesulfonainide, hydroxy anthracene,benzonaphthols, hydroxy-oenzo-lluorcnones, hydroxyazo compounds such as(o-hydroxyaniline resorcinol), coppered, and aniline 8- amino-Z-naphtholand the like, in addition to arylides of ,B-hydroxy aromatic andheterocyclic carboxylic acids. lliustratively, examples of such arylides(eg. anilides, etc.) which may be employed in the process of the instantinvention are Z-hydroxy-Z-naphthoic acid arylides, 3-hydroxyQ-anthroicacid arylides, 3-hydroXy-2-carbazole carboXylic acid arylides,2-hydroXy-3-dibenzofurane carboxylic acid arylides, Z-hydroXy-llH-benZo-(a)carbazole- 3-carboxylic acid arylides,hydroxydibenzothiophene carboxylic acid arylides and the like. These andother such coupling components operative herein are disclosed inDiserenes, Chemical Technology of Dyeing and ?rinting, volume 1, pages213 to 224 (Reinhold Publishing Corp, 1948); Lubs, Chemistry ofSynthetic Dyes and Pigments, pages 182 through 192 (Reinhold PublishingCorp, 1955), and Adams, Journal of the Society of Dyers and Colorists,volume 67, (1951) beginning at page 223. Those coupling component-scontaining an aromatically bound free amino group enable the attainmentof further improved results. Typical amino substituted couplers includeaminonaphthols, such as lamino-7-naphthol, l-amino-S-naphthol, and8-amino-lnapthol-3,6 di(ethylsulfonamide); amino-phenols, such asm-diethylaminophenol, aminoresorcinol, m-aminophenol; aminoazophenolsand naphthols, such as 6-hydr0xy-4-(onitrophenyl-azo)-1-naphthyl-amine;aminophenylpyrazolones, such as methyl mand p-aminophenylpyrazolone;acylacetarylides substituted in the aryl radical by an amino group, suchas acetoacet-rn-toluylene-diamine; o-hydroxycarboxylic acid arylideshaving an amine substituent in the .aryl radical, such as3-amino-3-hydroxy-2-naphthanilide.

The diazotization of the 2-aminophenoldisulfonamide is carried out inknown manner as by treatment with sodium nitrite and dilute hydrochloricacid. Similarly, the coupling reaction is carried out in known manner,usually in an alkaline solution at temperatures which may range from Oto 50 C.

The azo dyesuifs are then treated with an agent yielding chromium orcobalt in known manner in acid, neutral or alkaline media with orwithout the use of pressure and/or elevated temperatures. These agentsmay be applied in the form of their soluble or dispersed oxides,hydroxides or salts, as for example, with inorganic or organic acidssuch as hydrochloric, sulfuric, hydrofluoric, formic, acetic, tartaric,salicylic acids or the like. The metallizing agent may be used alone orin the presence of an additional substance. Such substance must notcause the metal ion to precipitate under the conditions of use. Thesesubstances may or may not form a complex compound with the metallizingagent, as for example, ammonia, pyridine, ethylene diamine,ethanolamine, formamide, formic acid, acetic acid, oxalic acid,aliphatic and aromatic hydroxy-containing compounds such as alcohol,glycerin, aliphatic hydroxy carboxylic acids such as tartaric, lacticand citric acids and the like, sugars, cellulose derivatives, phenols,tannins and lignins and the like, slouble salts of sulfonic acids andcarboxylic acids of the aliphatic, aromatic and hydroaromatic series,alkali metal and alkaline earth metal salts, oxides and hydroxides andthe like. Dispersing agents, solvents and other assistants may also beemployed in the metallizing process.

The metallization may be conducted with one or several metallizingagents simultaneously or successively to yield mixed metalliferouscomplex azo compounds in accordance with this invention. The metallizingagent may be applied in such manner that the resulting product is one ora mixture of complex compounds of the azo dyestufi containing one atomof metal in complex union with one to two azo dyestufi molecules,depending upon the valence and complex-forming characteristics of themetal, the particular dyestufi employed, the reaction conditions, thedesired properties, and the like. The preferrred ratio is one atom ofmetal to 2 molecules of dyestuffs, as produced in the examples below.

Since the pre-metallized azo dyestuffs of the instant invention aresubstantially water-insoluble, they are preferably converted to adispersed form for application to textile fibers from an aqueous dyebath. The dispersion of these insoluble products may be carried out bymixing the pre-metallized dye with at least an equal amount of asuitable dispersing agent such as a naphthalene formaldehyde sulfonicacid condensation product, and kneading the mixture in aWerner-Pficiderer mixer for several hours. In addition to dyeing textilefibers from an aqueous dispersion, the instant dyestuffs may also beemployed for coloring or pigmenting natural or artificial resins, orplastics in bulk, organic solvents, stains, varnishes, lacquers and thelike.

The following examples are illustrative of the instant invention and arenot to be regarded as limitative. All parts and proportions referred toherein and in the appended claims are by weight unless otherwiseindicated.

Example 1 Slurry 23.5 g. Z-aminophenolbis (ethylsulfonamid) in 250 cc.water and add 15 cc. hydrochloric acid 20 B. Cool to 10 C. with ice. Todiazotize, add 5.1 g. sodium nitrite (as solution) as rapidly as takenup as indicated by a spot on starch-iodide paper. When the diazo isready, pour into a solution of 13.2 g. phenylmethylpyrazolone in 250 cc.water containing 5 g. sodium hydroxide and 25 g. sodium carbonate andwhich has been cooled to to C. by the addition of ice. When the couplingis complete, the pH is reduced to about 4.5 and salt is added ifnecessary and the product is collected on a filter. The paste is thenslurried in 250 cc. water and the pH is increased to about 8.5 to 9.0 bythe addition of sodium carbonate. To this slurry is added a solution ofsodium chrome salicylate containing 2.3 g. Cr O and the whole heated to100 C. for 2 to 3 hours. The mixture is cooled to 25 to 30 C. and aceticacid is 4 added to pH 4.5 to 5.0 and the solid is filtered oil anddried.

The product dyes wool from a neutral to slightly acid bath pleasingshades of red of good fastness properties.

Example 2 If in Example 1 the phenylmethylpyrazolone is replaced by 28g. of l-amino 8 naphtholbis-3,6-(diethylsulfonamide), a dye is obtainedwhich dyes wool from a neutral to slightly acid bath greenish blueshades.

Example 3 If in Example 1 the phenylmethylpyrazolone is replaced by 11g. of Z-napthol, a dye is obtained which dyes wool from a neutral toslightly acid bath reddish blue shades.

Example 4 If in Example 1 the phenylmethyl pyrazolone is re placed by15.2 g. S-acetylamino-Z-naphthol, a dye is obtained which dyes wool froma neutral to slightly acid bath bluish gray shades.

Example 5 If in Example 1 the phenylmethylpyrazolone is replaced by 18.5g. of 2,5-dichlorophenylmethylpyrazolone, a dye is obtained which dyeswool from a neutral to slightly acid bath red shades.

Example 6 If in Example 1 the phenylmethylpyrazolone is replaced by 18.3g. of m-(3-methyl-5-oxo-2-pyrazolin-l-yl) .benzenesulfonamide, a dye isobtained which dyes wool in reddish shades from a neutral to slightlyacid bath.

Example 7 Slurry 23.5 g. 2-aminophenolbis (ethylsulfonamid) in 250 cc.water and add 15 cc. hydrochloric acid 20 B. Cool to 10 C. with ice. Todiazotize, add 5.1 g. sodium nitrite (as solution) as rapidly as takenup as indicated by a spot on starchiodide paper. When the diazo isready, pour into a solution of 13.2 g. phenylmethylpyrazolone in 250 cc.water containing 5 g. sodium hydroxide and 25 g. sodium carbonate andwhich has been cooled to 0 to 5 C. by the addition of ice. When thecoupling is complete, the pH is reduced to about 4.5 and salt is addedif necessary and the product is collected on a filter. Add paste to 250cc. water and add 8.8 g. cobalt chloride crystals. Increase pH to 8.5 to9.0. Heat to 40 to 45 C. for one hour. Reduce pH to 3.5 to 4.0 andfilter at 25 to 30 C.

The resulting dyestufif dyes wool brown shades from a neutral toslightly acid bath.

Example 8 If in Example 7, the phenylmethylpyrazolone is replaced with11 g. of Z-naphthol, a dyestuft' is obtained which dyes wool a reddishblue shade from a neutral to slightly acid bath.

Example 9 If in Example 7, the phenylmethylpyrazolone is replaced with18.5 g. 2,5dichlorophenylmethylpyrazolone, a dye-stuff is obtained whichdyes wool in a brown shade from a neutral to slightly acid bath.

Example 10 If in Example 1 the 2-aminophenolbis (ethylsulfonamid) isreplaced by 23.5 g. 2-aminophenolbis (dimethylsulfonamid) a dye isobtained which dyes wool from a neutral to slightly acidic bath in redshades.

Example 11 If 'in Example 1 the 2-aminophenolbis (ethylsulfonamid) isreplaced by 20 g. Z-aminophenolbis-(sulfonamid) a dye is obtained whichdyes wool from a neutral to slightly acidic bath in reddish shades.

amaze? Example 12 If in Example 1 the Z-aminophenolbis(ethylsulf-onamid) is replaced by 34 g.Z-aminophenolbis-(sulfonmorpholide) a dye is obtained which dyes woolfrom a neutral to slightly acidic bath in reddish shades.

Example 13 If in Example 1 the phenylmethylpyrazolone is replaced by13.4 g. acetoacetanilide a dye is obtained which dyes '00). from aneutral to slightly acidic bath in yellowish shades.

This invention has been disclosed with respect to certain preferredembodiments, and various modifications and variations thereof willbecome obvious to the person skilled in the art. It is to be understoodthat such modifications and variations are to be included within thespirit and scope of this application.

This application is a continuation-in-part of our application Serial No.704,312, filed December 23, 1957.

We claim:

1. The complex compound of 1 atom of chromium with 2 molecules of an2120 dyestuif devoid of free sulfonic and carboxylic acid groups andhaving the formula 53 wherein:

(1) R is selected from the group consisting of H and lower alkyl of nomore than 6 carbon atoms; (2) R is lower alkyl of no more than 6 carbonatoms;

and (3) Pz represents the radical of a 5-pyrazolone coupling componentcoupled in 4-position. 2. A compound as defined in claim 1 wherein R isH and R is ethyl.

3. A compound as defined in claim 2 wherein Pz represents the radical of1-phenyl-3-methyl-5-pyrazolone.

References Cited in the file of this patent UNITED STATES PATENTS1,908,571 Straub et al. May 9, 1933 2,551,056 Schetty May 1, 19512,711,404 Schetty June 21, 1955 2,723,263 Kuster et al. Nov. 8, 19552,723,372 Kuster et al Jan. 24, 1956 2,804,454 Betta Aug. 27, 19572,817,655 Schetty et a1 Dec. 24, 1957 2,979,503 Armento et a1 Apr. 11,1961 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Rat-cut N00 3O78 ,267 February 19 a 1963 William H Armento et alo It is herebycertified that error appears in the above numbered patent requiringcorrection and that the said Letters Patent should read as correctedbelow.

Column 6,, line 19 for "2 723,372".read 2 732,372

Signed and sealed this 5th day of November 1963a (SEAL) Attest:

EDWIN Lo REYNOLDS ERNEST W8 SWIDER Attesting Offiei-f ActingCommissioner of Patents

1. THE COMPLEX COMPOUND OF 1 ATOM OF CHROMIUM WITH 2 MOLECULES OF AN AZODYESTUFF DEVOID OF FREE SULFONIC AND CARBOXYLIC ACID GROUPS AND HAVINGTHE FORMULA